NSF - Summer Institute on Nano Mechanics and Materials

Surface Engineering and

Coatings
Ali Erdemir
Argonne National Laboratory
Energy Technology Division
Tribology Section
Argonne, IL 60439
Ivan Petrov
Center for Microanalysis of Materials
Frederick Seitz Materials Research Laboratory
University of Illinois
104 S. Goodwin Avenue
Urbana, IL 61801
Lecture 1
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Course Outline

Mon 8:30-12:00

Mon 1:00-4:30 pm

L1: Introduction to Surface Engineering and Coating Processes (PVD, CVD,

Ion-Beam and Other Techniques)
L2: Fundamentals of Vacuum Science and Technology (Plasma Physics
and Chemistry, Surface Interactions)
L3: Fundamentals of Sputter Deposition

L4: Fundamentals of Nucleation and Growth

L5: Computational Methods: Atomistic and Molecular Dynamics Simulation
of Film Growth
P1: Lab tour: Thin film deposition and surface engineering facilities (MSE)

Tue 8:30-12:00

L6: Recent Advances in Surface Cleaning and Preparation Techniques

L7: Recent Advances in Surface Engineering and Coating Technologies
L8: Hybrid Coatings and Deposition Processes

Tue 1:00-4:30 pm

L9: Novel Coating Architectures (Nano-structured and -composite films

(superlattice; compositionally/structurally modulated systems,
hybridization of coatings with surface texturing and/or patterning)
L10: Scale-up and Design; Industrial Systems and Practices
P2: Hands-on with Plasma Deposition Processes
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Outline Contd

Wed 8:30-12:00

- L11: Introduction to Thin Film Characterization

- L12: Surface Characterization (physical and chemical methods, XPS,
AES, SIMS, etc)
- L13: Structural Characterization (TEM, SEM, etc.)
Wed 1:00-4:30 pm

- L14: Mechanical Characterization (Adhesion, Hardness, Elastic

Properties, Toughness, etc.)
- P3: Lab Tour: Surface and Structural Characterization Facilities
- P4: Practical Experience with Some of the Characterization Methods
(SEM, TEM, AFM, etc.)
Thu 8:30-12:00

- L15: Tribological Characterization

- L15: An Overview of Emerging Technologies
- L16: Superhardness and superlubricity: theory and experiments
Thu 1:00-4:30 pm

- L17: Classification and Industrial Applications of Coatings

- P4: Lab Tour: Tribology Test Facilities (ME)
- P5: Hands-on Nano-indentation, Tribology
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Outline Contd

Fri 8:30-12:00

- L18: Guest Speaker 1: Dr. K. Wahl, NRL

Nanomechanics and tribology of coatings
- L19: Guest Speaker 2: Prof. Y.-W. Chung, NSF.
Applications of Tribological Coatings in Extremely High-Density
Computer Disk Drive Applications
- L20: Guest Speaker: Dr. Jeffrey Sanders, AFRL/MLBT
Advanced Materials and Coatings for Aerospace Applications

Tentative Lab Tours

Material Science & Engineering

Mechanical Engineering
NUANCE Microscopy Facility
Surface Electron & X-Ray Diffraction
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L1: INTRODUCTION TO SURFACE

ENGINEERING AND COATING
PROCESSES

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Surface Engineering

Definition: Modification of near-surface

structure, chemistry or property of a
substrate in order to achieve superior
performance and/or durability. It is an
enabling technology and can impact a wide
range of industrial sectors.

Examples of Surface
Engineering Processes

- Combining chemistry, physics, and

mechanical engineering with
metallurgy and materials science, it
contributes to virtually all
engineering disciplines.
- It can be done on a given surface
by metallurgical, mechanical,
physical, and chemical means, or
by producing a thick layer or a thin
coating.
- Both metallic and non-metallic
surfaces can be engineered to
provide improved property or
performance.
Multilayer
Coatings

Coated
Textured

Examples of
Engineered Surfaces

Plasma
Spray
Coating

Nitrided
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What are the benefits and where are they used?

Specific properties rely on surfaces

Cutting
- Wear, friction, corrosion, fatigue, reflectivity, emissivity,
color, thermal/electrical conductivity, bio-compatibility, etc.
Benefits
- Extend product life (durability)
- Improve resistance to wear, oxidation and corrosion
(performance)
Forming
- Satisfy the consumer's need for better and lower cost
components
- Reduce maintenance (reliability and cost)
Decoration
- Reduce emissions and environmental waste
- Improve the appearance; visually attractivity
- Improve electrical conductivity
Bio-medical
- Improve solderability
- Metallize plastic component surfaces
- Provide shielding for electromagnetic and radio frequency
radiation.
By improving durability, it reduces waste of natural
resources and energy.
Surface engineered automotive parts and components
can extend warranties and reduce emissions. For
Automotive
example: A hardened engine valve will last a minimum of
five years without replacement.
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Scales of Surface Engineering

Surface engineering technologies span:

- Five orders of magnitude in

thickness
- It can vary from several mm for
weld overlays to a few atomic
layers or nanometers for
physical vapor deposition (PVD)
and chemical vapor deposition
(CVD) coatings or ion
implantation. Atomic-layer
deposition is also possible.
- Three orders of magnitude in
hardness
- Example of coating hardness
range from 250-300 Hv for soft
metal or spray coatings, 3500
Hv for Titanium Nitride PVD
coatings and up to 10,000 Hv for
diamond coatings
- Almost infinite possibilities in the
range of compositions and/or
microstructure
Nano-composite, nano-layered,
amorphous, crystalline, quasiPioneering
crystalline, etc.
Science and

Superlattice
Coatings

Duplex
Coatings

~1 mm thick
Multilayer
Coatings
Thermal Spray
Coating
Superhard
CVD-Diamond
Films

Technology

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Evolution and Significance of Surface Engineering

-

It is an enabling technology
It can combine various surface
treatments with thin film and
coating deposition.
It can substantially improve wear
and corrosion resistance of
structural components.
It increases component lifetime
and resistance to aggressive
environments.
It can produce functional coatings
that modify biocompatibility and
optical and electrical properties of
critical components
Single component (1980s)

Evolution of
Coating
Architectures
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Multicomponent, Multilayer (1990s)

(2000 and beyond)

Nanostructured,
Superlattice, Gradient

Adaptative (smart)

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Classification of Surface Engineering Processes

The traditional, well established

processes:
- Painting
- Electroplating
- Galvanizing
- Thermal and plasma spraying
- Nitriding. Carburizing, Boriding
The more technologically advanced
coating technologies:
- Physical and chemical vapor
deposition
- Ion implantation
- Ion-assisted deposition
- Ion-beam mixing
- Laser treatment
Nowadays, a multitude of options are
available to select and specify a
treatment or a combination of
treatments to engineer the surfaces
of components or structures.

Plasma
Nitriding

Plasma
Spray

Plasma-source
Ion Implantation

CVD
Ion-beam
deposition

PVD

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Classification of Various Coating Methods

SURFACE COATING METHODS

Gaseous State
CVD

PVD

IBAD

Plasma variants

Major Emphasis of
This Course

Molten or semimolten State

Solution State
Chemical
solution
deposition

Chemical
reduction

Electrochemical
deposition

Electroless
deposition

Sol gel

Chemical
conversion

Laser

Thermal
spraying

Plasma variants

K.Holmberg, A. Matthews, Coatings Tribology,

Ed.D.Dowson, Tribology Series, 28, Elsevier, 1994.

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Physical Vapor Deposition (PVD)

Chemical Vapor Deposition (CVD)

Are special methods by which a

protective hard or soft film can
be produced

- Preferably on the outer

surfaces of a machine
element
- Desired results: superior
performance, protection,
durability.
Various engine parts treated by PVD
Gear systems

Multilayer CVD coatings

Cutting and forming tools12
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CVD and PVD: Enabling Surface Technologies

Processes

CVD/PVD can effectively modify nearsurface structure and/or chemistry of

mechanical parts or components and
hence improve their performance and
increase their durability/reliability.
As enabling technologies, they can
impact a wide range of industrial
sectors.
Both metallic and non-metallic
surfaces can be engineered by CVD
and PVD.

Diamond

Multi-layer

Applications

Products

Nano-composite or
-structured
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MODERN PRACTICES IN PVD AND CVD

ARC-PVD

PACVD

One Process
One System
Many Coating Solutions

CCplusC

TiAlN

TINALOX

TiCN

DLC

MoS2

TIN

B4C

c
Make
Your
Choice

CBN

MultiLayer

CrN
WC-C
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TiB2

ALOX

Courtesy of CemeCon, GMBH

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Large-scale Systems

In-line PVD

Sputtering

Arc-PVD
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CVD

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Physical Vapor Deposition (PVD)

Thermal Evaporation

PVD: A type of vacuum

deposition process where a
material is vaporized in a
vacuum chamber, transported
atom by atom across the
chamber to the substrate, and
condensed into a film at the
substrate's surface.
Ion Beam Sputtering

Film

Magnetron Sputtering

<W>=4.88nm

It provides
the kind of super-critical, non-equilibrium chemical/physical states needed
for the
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of new coatings with unusual properties, such as super-hardness or -low U.S.
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Classification of PVD
Physical Vapor Deposition (PVD)

Evaporative PVD
Resistive

Sputtering PVD
Diode

Inductive

Magnetron

Electron
Beam Gun

Ion Beam
Triode

Arc
Laser

K.Holmberg, A. Matthews, Coatings Tribology, Ed.D.Dowson, Tribology Series, 28, Elsevier, 1994.
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Examples of Plasma-based PVD Processes

Ion plating

Activated reactive evaporation

Bias sputter deposition

Ion-beam assisted
deposition

Cathodic arc deposition

Dual ion-beam sputtering

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Evaporative PVD Processes

EB Evaporation PVD
Thermal Evaporation PVD
Laser Evaporation or
Ablation

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Sputter Deposition
Basics:
A voltage is applied across a rarified gas.
Breakdown of the gas forms a glow
discharge plasma.
Positive ions from the plasma strike the
negative electrode.
Energy from the ions is transferred to
target atoms.
A few of these may escape from the
target surface (they are sputtered).
The sputtered atoms condense on the
substrate forming a film.
Magnetron: a device in which a magnet system
on the back of the cathode deflects the
electrons, thus lengthening the ionization path.
The accelerated ions transfer their momentum
to particles of the coating material, which
are then deposited on the substrate.

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Magnetron

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Various Sputtering Methods

Schematic representation

Cold Cathode DC Diode

sputtering
DC triode Sputtering
AC Sputtering
Rf Sputtering
DC Magnetron Sputtering
- Unbalanced Magnetron
- Balanced Magnetron
- Pulsed DC Magnetron
- Ion and Plasma Beam
Sputtering

Ion-beam sputtering
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Sputtering Mechanism
Bombardment of solid (target) by high
energy chemically inert ions (e.g. Ar+)
That are extracted from plasma.
Such bombardment causes ejection
of atoms from the target which are then
re-deposited on the surface of the
substrate purposely located in the
vicinity of the target.

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Diode vs Magnetron Sputtering

Diode

Comments:
Simple, relative ease in
fabrication and thickness
uniformity over large area
Realtively high deposition
pressure and relatively
high substrate temperature
Magnetron

Comments:
High deposition rates, low
deposition pressure, low
substrate temperature, can be
scaled up, so commonly used
for industrial production
More complex than planar
diode systems
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Ion Beam Sputtering

Dual-ion-beam sputtering

A physical vapor deposition process in which

the coating material (target) is removed from
the surface of the coating source (cathode) by
a flux of high energy ions and deposited upon
the surface of substrates.
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It can also be used to sputter-off or

clean substrate surface
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ARC PVD

Main Characteristics
- High Vaporization Rate
- High Ionization Rate
- High Throughputs
- High Deposition Rate
- Strong film/substrate
bonding

Micro/macro-droplets
May cause problems

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PVD, CVD Systems

Nitride coatings (TiN, CrN, ZrN)
Carbide and Carbonitride coatings
(TiC, TiCN)
Multicomponent Coatings
(TiAlN)
DLC and Diamond Coatings etc.
Thickness: 1 to 100 microns
Operating Temperature : RT to 500-600 C

Arc PVD
Sputtering PVD

rf CVD
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FILTERED ARC

The filtered cathodic arc may be used to produce a range coatings

It reduce/eliminate microdroplets associated with conventional arc evaporation
High deposition rates are available for most materials and compounds
It does not promote/cause poisoning of the cathodes in reactive deposition
It provides very ionization
It is cheaper than electron beam methods
It is suitable for most metals including high temperature materials (Ta,W,C)
It cannot be used for evaporating semi-/ or di-electric materials
It cannot be used for evaporating low heat conductivity materials
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Ion Beam Assisted Deposition

It is a vacuum-deposition process
that combines physical vapor deposition
(PVD) with ion-beam bombardment .
A vapor of coating atoms is generated
with an electron-beam evaporator and
deposited on a substrate. Ions, typically
gaseous, are simultaneously extracted
from a plasma and accelerated into the
growing PVD film at energies of several
hundred to several thousand
electronvolts (eV).

Good for high-value added applications or science

Difficulty in scaling-up
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Chemical Vapor Deposition (CVD)

Plasma Enhanced CVD

Conventional CVD

CVD is a process in which

the gaseous species are
transported to the reaction
chamber, activated
thermally or by a plasma in
the vicinity of the
substrate, and made to
react to form a solid
deposit on the substrate
surface (R. F. Bunshah)
CVD is a relatively mature
technique
Used in electronic,
optoelectronic, tooling
industry, ceramic fiber
production etc,

As in DLC Coatings

Hot-filament CVD

It is possible to deposit
films of uniform thickness
and low porosity even on
substrates of complicated
shape in CVD.
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Classification of CVD
Chemical Vapour Deposition (CVD)

Chemical Vapor Infiltration

Metal Organic
Vapor Phase Epitaxy

Metal - Organic
Hot Filament
Laser Assisted
Electron Assisted
Low Pressure
Normal Pressure

Plasma- Assisted
Atomic Layer Epitaxy

DC

Pulse

AC

rf

Microwave

Plasma

Plasma

Plasma

Plasma

Plasma

K.Holmberg, A. Matthews, Coatings Tribology, Ed.D.Dowson, Tribology Series, 28, Elsevier, 1994.
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The Gas-Phase Chemistry of CVD Processes

Thermal-Decomposition Reactions:
- Hydrocarbon Decomposition CH4(g) C(s)+2H2(g)
- Halide Decomposition
WF6(g) W(s)+3F6(g)
- Carbonyl Decomposition
Ni(CO)4(g) Ni(s)+4CO(g)
- Hydride Decomposition
SiH4(g) Si(s)+2H2(g)
Hydrogen Reduction:
CVD TiN and TiC Coated Tool Inserts
SiCl4(g)+2H2(g) Si(s)+4HCl(g)

Co-reduction:
TiCl4(g)+2BCl3(g)+5H2(g) TiB2(s)+10HCl(g)

Reactions Leading to Carbide and

Nitride Formation:
TiCl4(g)+CH4(g) TiC(s)+4HCl(g)
3SiCl4(g)+4NH3(g) Si3N4(s)+12HCl(g)
CVD is able to produce single or multilayer coatings with composite or nanostructured
architectures. It is not a line of sight process, hence allows the coating of complex shaped
engineering components. Major drawbacks: Safety issue (hazardous, flammable gases),
high-temperature requirement.
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Example of Plasma Assisted CVD

Plasma-enhanced CVD

Used in
Deposition
Of DLC

Hot-filament CVD
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Chemical/Physical Events
That Control Nucleation
and Growth
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Future Directions in PVD and CVD Processes

1980s

2000s

1900s
Single component

Smart
Processes
(hybrids, etc.)

Multicomponent, Multilayer
Nanostructured,
Superlattice, Gradient
Textured, Adaptive (smart)

Novel Coating Architectures for the 21st Century

Nano-composite
coatings

Sculptured Coatings

Superlattice and/or multi-layer coatings

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Key References

ASM Handbook: Surface Engineering, by Faith Reidenback, ASM-International,

Metals Park, OH, 1994
Surface Engineering: Fundamentals of Coatings by P. K. Datta and J. S. Gray,
Royal Society of Chemistry, 1993
Chemical Vapor Deposition (Surface Engineering Series, V. 2)
by J.-H. Park and T. S. Sudarshan, ASM-International, Metals Park OH, 2001.
Chemical vapour deposition of coatings by K.L. Choy, Progress in Materials
Science, 48 (2003) 57170.
Advanced Surface Coatings: A Handbook of Surface Engineering, by D. S.
Rickerby, A. Mathews, Blackie Academic and Professional Publ. 1991.
Handbook of Hard Coatings, by R. F. Bunshah, William Andrew
Publishing/Noyes, 2001.
Handbook of Physical Vapor Deposition (PVD) Processing by
D. M. Mattox, William Andrew Publishing/Noyes, 1998.
Handbook of Thin-Film Deposition Processes and Techniques - Principles,
Methods, Equipment and Applications, by K. Seshan, William Andrew
Publishing/Noyes, 2002.
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